US20220064075A1 - Porous ceramic structure - Google Patents
Porous ceramic structure Download PDFInfo
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- US20220064075A1 US20220064075A1 US17/444,197 US202117444197A US2022064075A1 US 20220064075 A1 US20220064075 A1 US 20220064075A1 US 202117444197 A US202117444197 A US 202117444197A US 2022064075 A1 US2022064075 A1 US 2022064075A1
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- porous ceramic
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- ceramic structure
- containing particles
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- 239000000919 ceramic Substances 0.000 title claims abstract description 93
- 239000002245 particle Substances 0.000 claims abstract description 156
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 21
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 76
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 72
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 72
- 239000000126 substance Substances 0.000 claims description 14
- 239000006104 solid solution Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 34
- 239000001301 oxygen Substances 0.000 description 34
- 229910052760 oxygen Inorganic materials 0.000 description 34
- 230000003197 catalytic effect Effects 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- 238000005192 partition Methods 0.000 description 25
- 239000007789 gas Substances 0.000 description 24
- 238000003860 storage Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910004288 O3.5SiO2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002276 dielectric drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Definitions
- the present invention relates to a porous ceramic structure.
- a porous ceramic structure having a honeycomb structure has conventionally been used as a catalytic converter for use in processing for cleaning hazardous substances such as HC, CO, and NO x contained in an exhaust gas exhausted from an engine of an automobile or other vehicles.
- a porous ceramic structure may be subjected to, for example, a coating process using ⁇ -alumina in order to increase a specific surface area and thereby increase the amount of a catalyst supported, but such a coating process may increase pressure loss in the structure.
- Japanese Patent Application Laid-Open No. 2017-171543 proposes a technique that eliminates the need for the aforementioned coating process by exposing part of cerium dioxide particles from the surfaces of pores in a honeycomb structure and causing the cerium dioxide particles to support fine catalytic particles of an element of the platinum group.
- the cerium dioxide particles have oxygen storage and release capability and act as promoters that reduce variations in air-fuel ratio in an exhaust gas by storing or releasing oxygen and thereby maintain high catalytic activity of fine catalytic particles.
- the present invention is intended for a porous ceramic structure, and it is an object of the present invention to improve promoter activity in the porous ceramic structure.
- a porous ceramic structure includes a porous structure body composed primarily of cordierite, and Ce- and Zr-containing particles containing Ce and Zr and fixedly attached to the structure body.
- the Ce- and Zr-containing particles have a fixedly attached portion located inside the structure body, and a protrusion contiguous with the fixedly attached portion and protruding from the structure body.
- a total content of Ce and Zr is higher than or equal to 6.0% by mass and lower than or equal to 20% by mass in terms of CeO 2 and ZrO 2 .
- a Ce content is higher than or equal to 5.0% by mass and lower than or equal to 15% by mass in terms of CeO 2 .
- a Zr content is higher than or equal to 1.0% by mass and lower than or equal to 5.0% by mass in terms of ZrO 2 .
- At least part of Ce exists as CeO 2 .
- At least part of Zr is dissolved as a solid solution in CeO 2 .
- a ratio of an amount of substance of Zr to a total amount of substances of Ce and Zr in CeO 2 with Zr dissolved therein as a solid solution is higher than or equal to 10% and lower than or equal to 20%.
- the Ce- and Zr-containing particles have an average particle diameter greater than or equal to 10 nm and less than or equal to 2 ⁇ m.
- catalyst particles are supported by the Ce- and Zr-containing particles.
- FIG. 1 is a perspective view of a porous ceramic structure
- FIG. 2 is a schematic diagram illustrating part of a partition wall in enlarged dimensions.
- FIG. 3 shows an SEM image of the surface of the partition wall
- FIG. 4 is a sectional view of an area in the vicinity of a Ce- and Zr-containing particle.
- FIG. 1 is a perspective view illustrating a porous ceramic structure 1 according to one embodiment of the present invention.
- the porous ceramic structure 1 is a catalyst carrier for cleaning an exhaust gas used in the purification of an exhaust gas exhausted from an engine.
- the number of cells 13 illustrated, which will be described later, is smaller than an actual number.
- the porous ceramic structure 1 includes a honeycomb structure 10 serving as a porous structure body, and Ce- and Zr-containing particles fixedly attached to the honeycomb structure 10 .
- the Ce- and Zr-containing particles are fine particles containing cerium (Ce) and zirconium (Zr).
- the Ce- and Zr-containing particles support oxidation catalyst particles such as the aforementioned precious metal (e.g., elements of the platinum group such as platinum (Pt) or palladium (Pd)).
- oxidation catalyst particles such as the aforementioned precious metal (e.g., elements of the platinum group such as platinum (Pt) or palladium (Pd)).
- fine particles other than the Ce- and Zr-containing particles may be fixedly attached to the honeycomb structure 10 , in addition to the Ce- and Zr-containing particles.
- the honeycomb structure 10 includes a tubular outer wall 11 and a partition wall 12 .
- the tubular outer wall 11 has a tubular shape extending in a longitudinal direction (i.e., substantially the right-left direction in FIG. 1 ).
- the tubular outer wall 11 may have a circular shape in cross section perpendicular to the longitudinal direction, and may have any other shape such as a polygon.
- the partition wall 12 is provided in the interior of the tubular outer wall 11 and partitions the interior into a plurality of cells 13 .
- the honeycomb structure 10 is a cell structure whose interior is partitioned into a plurality of cells 13 by the partition wall 12 .
- the tubular outer wall 11 and the partition wall 12 are each made of a porous material.
- the partition wall 12 has, for example, a thickness greater than or equal to 50 micrometers ( ⁇ m), preferably greater than or equal to 100 ⁇ m, and more preferably greater than or equal to 150 ⁇ m. From the viewpoint of reducing pressure loss in the partition wall 12 , the thickness of the partition wall 12 is, for example, less than or equal to 500 ⁇ m and preferably less than or equal to 450 ⁇ m.
- Each cells 13 is a space extending in the longitudinal direction and forms a flow path that passes an exhaust gas from an engine.
- the cells 13 may have a polygonal (e.g., triangular, quadrangular, pentagonal, or hexagonal) shape in cross section perpendicular to the longitudinal direction, and may have any other shape such as a circle.
- the cells 13 typically have the same cross-sectional shape.
- the cells 13 may include cells 13 that have different cross-sectional shapes.
- the density of the cells is, for example, higher than or equal to 8 cells per square centimeters (cells/cm 2 ) and preferably higher than or equal to 15 cells/cm 2 .
- the cell density is, for example, lower than or equal to 95 cells/cm 2 and preferably lower than or equal to 78 cells/cm 2 .
- the honeycomb structure 10 is composed primarily of cordierite (2MgO.2Al 2 O 3 .5SiO 2 ).
- the honeycomb structure 10 may be composed of only cordierite, or may contain other materials different from cordierite (e.g., metal or ceramic other than cordierite).
- the content of cordierite in the honeycomb structure 10 is, for example, higher than or equal to 75% by mass and preferably higher than or equal to 80% by mass.
- the honeycomb structure 10 is substantially composed of only cordierite.
- the partition wall 12 of the honeycomb structure 10 has, for example, an open porosity higher than or equal to 25%, preferably higher than or equal to 30%, and more preferably higher than or equal to 35%.
- the open porosity of the partition wall 12 is, for example, lower than or equal to 70% and preferably lower than or equal to 65%.
- the open porosity can be measured by, for example, the Archimedes method using deionized water as a medium.
- the partition wall 12 of the honeycomb structure 10 has, for example, a mean pore diameter greater than or equal to 5 ⁇ m and preferably greater than or equal to 8 ⁇ m. Like the open porosity, pressure loss in the porous ceramic structure 1 decreases as the mean pore diameter of the partition wall 12 increases. From the viewpoint of improving catalytic activity in the porous ceramic structure 1 , the mean pore diameter of the honeycomb structure 10 is, for example, less than or equal to 40 ⁇ m, preferably less than or equal to 30 ⁇ m, and more preferably less than or equal to 25 ⁇ m.
- the mean pore diameter can be measured by, for example, mercury porosimetry (compliant with JIS R1655).
- FIG. 2 is a schematic diagram illustrating part of the partition wall 12 of the porous ceramic structure 1 in enlarged dimensions.
- the aforementioned Ce- and Zr-containing particles 2 are fixedly attached to the surface of the partition wall 12 of the honeycomb structure 10 in an exposed manner.
- the surface of the partition wall 12 refers to the outer surface of the partition wall 12 (i.e., the surface surrounding the cells 13 ) and the inner surfaces of a large number of small pores in the partition wall 12 .
- the Ce- and Zr-containing particles 2 on the surface of the partition wall 12 are cross-hatched.
- fine catalytic particles 3 such as precious metal particles supported on the surface of the Ce- and Zr-containing particles 2 are also illustrated in FIG. 2 .
- the Ce- and Zr-containing particles 2 generally have particle diameters greater than the particle diameters of the fine catalytic particles 3 . Note that the particle diameters of the Ce- and Zr-containing particles 2 and the fine catalytic particles 3 in FIG. 2 are illustrated larger than actual particle diameters.
- the fine catalytic particles 3 are supported by the Ce- and Zr-containing particles 2 exposed to the surface of the partition wall 12 .
- This facilitates an increase in the amount of fine catalytic particles 3 supported, without increasing the specific surface area of the partition wall 12 by a conventional coating process (wash coating) using ⁇ -alumina. Therefore, it is possible to, for example, prevent an increase in pressure loss from being caused by a coating process using ⁇ -alumina. It is not an absolute necessity that all of the fine catalytic particles 3 are supported by the Ce- and Zr-containing particles 2 , and some of the fine catalytic particles 3 may be supported directly on the surface of the honeycomb structure 10 .
- FIG. 3 shows a scanning electron microscope (SEM) image of the surface of the partition wall 12 in the honeycomb structure 10 .
- the particulate Ce- and Zr-containing particles 2 (white portions in the image) are fixedly attached to the surface of the honeycomb structure 10 .
- the Ce- and Zr-containing particles 2 are fixedly attached to the grain boundaries of a large number of cordierite crystals 122 (gray portions in the image), which form the honeycomb structure 10 , and protrude (i.e., are exposed) from the surface of the honeycomb structure 10 to the surrounding space.
- FIG. 3 is an illustration of a state before the aforementioned fine catalytic particles 3 (see FIG. 2 ) are supported by the Ce- and Zr-containing particles 2 .
- FIG. 4 is a sectional view of an area in the vicinity of a Ce- and Zr-containing particle 2 on the surface of the partition wall 12 of the honeycomb structure 10 .
- the Ce- and Zr-containing particle 2 is in a form partly protruding from the inside of the honeycomb structure 10 to the surrounding space.
- the aforementioned fine catalytic particles 3 (see FIG. 2 ) supported on the Ce- and Zr-containing particles 2 are not illustrated.
- the Ce- and Zr-containing particle 2 has a fixedly attached portion 21 and a protrusion 22 .
- the fixedly attached portion 21 is located inside the honeycomb structure 10 .
- the language “inside the honeycomb structure 10 ” refers to inside the cordierite composing the honeycomb structure 10 and does not refer to the internal spaces of small pores provided in the honeycomb structure 10 .
- the fixedly attached portion 21 is a bonding portion of the Ce- and Zr-containing particle 2 that is bonded to the cordierite serving as the principal component of the honeycomb structure 10 and that is fixedly attached to the inside of the cordierite.
- the fixedly attached portion 21 is a portion of the Ce- and Zr-containing particle 2 that crawls into the cordierite from the surface of the honeycomb structure 10 to the side opposite to the space around the surface.
- the fixedly attached portion 21 is an area of the Ce- and Zr-containing particle 2 that has a surface covered with the cordierite.
- the fixedly attached portion 21 exists at a grain boundary of cordierite crystals 122 ( FIG. 3 ) in the honeycomb structure 10 and is fixedly attached to the grain boundary.
- the protrusion 22 is a portion of the Ce- and Zr-containing particle 2 that protrudes from the surface of the honeycomb structure 10 into the surrounding space.
- the protrusion 22 is a portion exposed from the surface of the aforementioned cordierite.
- the protrusion 22 protrudes from a grain boundary of cordierite crystals 122 into the surrounding space.
- the protrusion 22 is contiguous with the fixedly attached portion 21 .
- some of a large number of Ce- and Zr-containing particles 2 are fixedly attached to the surface of the honeycomb structure 10 as described above, and the other Ce- and Zr-containing particles 2 are located in their entirety inside the honeycomb structure 10 .
- substantially all of the Ce- and Zr-containing particles 2 may be fixedly attached to the surface of the honeycomb structure 10 . Since the honeycomb structure 10 is not subjected to a coating process using ⁇ -alumina or other materials as described above, there is no case that the Ce- and Zr-containing particles 2 are fixedly attached to the honeycomb structure 10 via a coating formed by such a coating process.
- the Ce- and Zr-containing particles 2 have, for example, an average particle diameter greater than or equal to 10 nm and less than or equal to 2 ⁇ m, preferably greater than or equal to 10 nm and less than or equal to 500 nm, and more preferably greater than or equal to 10 nm and less than or equal to 200 nm.
- the average particle diameter of the Ce- and Zr-containing particles 2 is an average particle diameter of the protrusions 22 of the Ce- and Zr-containing particles 2 that can be observed with an SEM.
- the average particle diameter of the Ce- and Zr-containing particles 2 is obtained by calculating an average value of the particle diameters of Ce- and Zr-containing particles 2 in an image of the Ce- and Zr-containing particles 2 captured with a predetermined magnification using an SEM or a field emission SEM (FE-SEM) or a transmission electron microscope (TEM).
- FE-SEM field emission SEM
- TEM transmission electron microscope
- a crystallite diameter of the Ce- and Zr-containing particles 2 obtained by X-ray diffraction (XRD) may be regarded as an average particle diameter of the Ce- and Zr-containing particles 2 .
- a total content of Ce and Zr in the porous ceramic structure 1 is, for example, higher than or equal to 6.0% by mass and lower than or equal to 20% by mass in terms of CeO 2 and ZrO 2 .
- the total content of Ce and Zr in the porous ceramic structure 1 is also simply referred to as a “total Ce/Zr content.”
- the total Ce/Zr content is preferably higher than or equal to 8.0% by mass and lower than or equal to 15% by mass in terms of CeO 2 and ZrO 2 .
- the total Ce/Zr content in terms of CeO 2 and ZrO 2 refers to the percentage of a value obtained by dividing the total mass of CeO 2 and ZrO 2 by the mass of the porous ceramic structure 1 on the assumption that all Ce components contained in the porous ceramic structure 1 exist as CeO 2 and all Zr components contained in the porous ceramic structure 1 exist as ZrO 2 .
- the content of Ce in the porous ceramic structure 1 is, for example, higher than or equal to 5.0% by mass and lower than or equal to 15% by mass in terms of CeO 2 .
- the content of Ce in the porous ceramic structure 1 is also simply referred to as a “Ce content.”
- the Ce content is preferably higher than or equal to 7.0% by mass and lower than or equal to 12% by mass in terms of CeO 2 .
- the Ce content in terms of CeO 2 refers to the percentage of a value obtained by dividing the mass of CeO 2 by the mass of the porous ceramic structure 1 on the assumption that all Ce components contained in the porous ceramic structure 1 exist as CeO 2 .
- the content of Zr in the porous ceramic structure 1 is, for example, higher than or equal to 1.0% by mass and lower than or equal to 5.0% by mass in terms of ZrO 2 .
- the content of Zr in the porous ceramic structure 1 is also simply referred to as a “Zr content.”
- the Zr content is preferably higher than or equal to 2.0% by mass and lower than or equal to 4.0% by mass in terms of ZrO 2 .
- the Zr content in terms of ZrO 2 refers to the percentage of a value obtained by dividing the mass of ZrO 2 by the mass of the porous ceramic structure 1 on the assumption that all Zr components contained in the porous ceramic structure 1 exist as ZrO 2 .
- the Zr content in terms of ZrO 2 is, for example, higher than or equal to 10% and lower than or equal to 40% of the Ce content in terms of CeO 2 and is preferably higher than or equal to 20% and lower than or equal to 35% of the Ce content in terms of CeO 2 .
- At least some of Ce components contained in the porous ceramic structure 1 exist as CeO 2 .
- substantially a total amount of Ce contained in the porous ceramic structure 1 exists as CeO 2 .
- At least some of Zr components contained in the porous ceramic structure 1 are dissolved as a solid solution in CeO 2 .
- substantially all Zr components contained in the porous ceramic structure 1 are dissolved as a solid solution in CeO 2 .
- a ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO 2 with Zr dissolved therein as a solid solution is, for example, higher than or equal to 10% and lower than or equal to 20% (i.e., higher than or equal to 10 mol % and lower than or equal to 20 mol %). This ratio is preferably higher than or equal to 15% and lower than or equal to 20%.
- CeO 2 stores and releases oxygen due to a reaction expressed by Expression 1 below.
- the reaction from the left-hand side to the right-hand side in Expression 1 indicates the reaction of CeO 2 that releases oxygen
- the reaction from the right-hand side to the left-hand side indicates the reaction of CeO 2 that stores oxygen.
- CeO 2 has oxygen storage and release capability and acts as a promoter that reduces variations in air-fuel ratio in the exhaust gas by storing or releasing oxygen and thereby maintains high catalytic activity of the fine catalytic particles 3 (see FIG. 2 ).
- the porous ceramic structure 1 may be produced by any of various known methods.
- a structure raw material is prepared by weighing and mixing materials for the honeycomb structure 10 and materials for the Ce- and Zr-containing particles 2 .
- the materials for the honeycomb structure 10 are composed primarily of a raw material for cordierite that serves as an aggregate of the honeycomb structure 10 and include, for example, magnesium oxide (MgO), aluminum oxide (Al 2 O 3 ), or silicon oxide (SiO 2 ).
- the materials for the honeycomb structure 10 also include, for example, a bore-forming agent and a binder.
- the materials for the Ce- and Zr-containing particles 2 are, for example, CeO 2 and ZrO 2 .
- the amounts of time required for the dry mixing and the kneading described above may, for example, be 15 minutes and 30 minutes, respectively.
- the dry mixing time and the kneading time may be modified in various ways.
- CeO 2 and ZrO 2 are individually added to the aggregate and the like of the honeycomb structure 10 , but the method of the addition may be modified in various ways.
- a material generated by immersing Zr in CeO 2 and drying and firing a resultant compound may be added to the aggregate and the like of the honeycomb structure 10 .
- part of Zr may be dissolved as a solid solution in CeO 2 , or may adhere to CeO 2 .
- the aforementioned green body is molded into a columnar shape by a vacuum kneading machine or any other machine and then extruded and molded into a honeycomb compact of a honeycomb shape by an extruder.
- the honeycomb compact includes therein a grid-like partition wall that sections the honeycomb compact into a plurality of cells serving as flow paths for a fluid such as an exhaust gas. Note that the honeycomb compact may be molded by a molding method other than extrusion molding.
- the honeycomb compact is subjected to drying.
- the drying method include hot air drying, microwave drying, dielectric drying, reduced pressure drying, vacuum drying, and freeze drying, and may also include any combination of these drying methods.
- the honeycomb compact is subjected to microwave drying so as to evaporate approximately 50% to 80% of moisture, and is then subjected to hot air drying (at 60° C. to 100° C. for 6 to 20 hours).
- the honeycomb compact is subjected to microwave drying so as to evaporate approximately 70% of moisture, and is then subjected to hot air drying (at 80° C. for 12 hours).
- the honeycomb compact is put into a degreasing furnace that is maintained at 450° C. so as to remove (i.e., degrease) organic components remaining in the honeycomb compact.
- the honeycomb compact is subjected to a firing process (firing) so as to form the porous ceramic structure 1 including the honeycomb structure 1 and the Ce- and Zr-containing particles 2 .
- a firing process for example, the firing process is conducted at a firing temperature of 1300° C. to 1500° C. for 8 hours under atmospheric pressure.
- the firing temperature is preferably higher than or equal to 1350° C. and more preferably higher than or equal to 1370° C.
- the firing temperature is also preferably lower than or equal to 1450° C. and more preferably lower than or equal to 1430° C. Conditions for the firing process may be modified appropriately.
- the fine catalytic particles 3 are to be supported after the firing process described above.
- the content of each component (mass %) in the composition of the materials for the porous ceramic structure 1 was calculated through analysis based on inductivity coupled plasma (ICP) atomic emission spectroscopy.
- the content (mass %) of the Ce- and Zr-containing particles 2 refers to a total of the contents (mass %) of CeO 2 and ZrO 2 .
- the ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO 2 with Zr dissolved therein as a solid solution (hereinafter, also referred to as “solid solubility rate of Zr”) was obtained as follows. First, X-ray diffraction data obtained by measuring the porous ceramic structure 1 with an X-ray diffractometer (rotary anti-cathode X-ray diffractometer: RINT produced by Rigaku Corporation) was analyzed to obtain a lattice constant of CeO 2 . Then, calibration curves were created for lattice constants obtained in the same manner for samples having known solid solubility of Zr, and the solid solubility rate of Zr (mol %) was obtained using the calibration curves.
- X-ray diffraction data obtained by measuring the porous ceramic structure 1 with an X-ray diffractometer (rotary anti-cathode X-ray diffractometer: RINT produced by Rigaku Corporation) was analyzed to obtain a la
- the average particle diameter of the Ce- and Zr-containing particles 2 in the porous ceramic structure 1 is an arithmetical mean of the particle diameters of the Ce- and Zr-containing particles 2 measured from the aforementioned SEM image.
- the oxygen storage capability of the porous ceramic structure 1 was obtained as follows. First, the porous ceramic structure 1 was placed in a container, and a first gas containing oxygen (O 2 ) is supplied to the internal space of the container to oxidize the Ce- and Zr-containing particles 2 and store oxygen.
- the first gas was a mixed gas of O 2 and an inert gas such as nitrogen (N 2 ), and the content of O 2 in the mixed gas was assumed to be 20% by volume.
- the first gas was exhausted from the internal space of the container, and a second gas containing H 2 was supplied to the internal space and passed through a large number of cells 13 in the porous ceramic structure 1 .
- the second gas was a mixed gas of H 2 and an inert gas such as N 2 , and the H 2 content in the mixed gas was assumed to be 5% by volume.
- H 2 reacted with the oxygen released from the Ce- and Zr-containing particles 2 (i.e., oxygen stored in the Ce- and Zr-containing particles 2 as a result of supply of the first gas) to form H 2 O when passing through the cells 13 .
- the amount of H 2 O of the second gas passing through the porous ceramic structure 1 is measured by gas chromatography or other techniques, the amount of oxygen stored in the Ce- and Zr-containing particles 2 can be calculated from a resultant measurement value.
- Table 1 lists, as the oxygen storage capability of the porous ceramic structures 1 , the value obtained by dividing the amount of substance (mol) of O 2 calculated from the measurement value of H 2 O in the second gas by the amount of substance (mol) of Ce contained in the porous ceramic structures 1 .
- the Ce- and Zr-containing particles 2 have higher oxygen storage and release capability and, as described above, have a higher function of reducing variations in air-fuel ratio in the exhaust gas. That is, the Ce- and Zr-containing particles 2 exhibit higher promoter activity as the oxygen storage capability improves.
- Example 1 the CeO 2 content and the ZrO 2 content in the material composition were 6.1% by mass and 2.0% by mass, respectively.
- the ZrO 2 content was approximately one third of the CeO 2 content.
- the content of the Ce- and Zr-containing particles 2 was 8.1% by mass.
- the solid solubility rate of Zr was 17.2 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 55 nm.
- the oxygen storage capability was 0.0007 and high.
- Example 2 the CeO 2 content and the ZrO 2 content in the material composition were 7.9% by mass and 2.6% by mass, respectively.
- the ZrO 2 content was approximately one third of the CeO 2 content.
- the content of the Ce- and Zr-containing particles 2 was 10.6% by mass.
- the solid solubility rate of Zr was 18.3 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 120 nm.
- the oxygen storage capability was 0.0008 and high.
- Example 3 the CeO 2 content and the ZrO 2 content in the material composition were 9.6% by mass and 3.2% by mass, respectively.
- the ZrO 2 content was approximately one third of the CeO 2 content.
- the content of the Ce- and Zr-containing particles 2 was 12.9% by mass.
- the solid solubility rate of Zr was 17.8 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 630 nm.
- the oxygen storage capability was 0.0007 and high.
- Example 4 the CeO 2 content and the ZrO 2 content in the material composition were 11.3% by mass and 3.8% by mass, respectively.
- the ZrO 2 content was approximately one third of the CeO 2 content.
- the content of the Ce- and Zr-containing particles 2 was 15.0% by mass.
- the solid solubility rate of Zr was 17.2 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 1200 nm.
- the oxygen storage capability was 0.0006 and high.
- Example 1 to 4 show that the content of the Ce- and Zr-containing particles 2 increases in order of Examples 1 to 4 and the average particle diameter of the Ce- and Zr-containing particles 2 increases in the order of Examples 1 to 4.
- the amount of storage of oxygen and the amount of release of oxygen, caused by the reaction expressed by Expression 1 above increase and accordingly the oxygen storage capability improves.
- the surface area of the Ce- and Zr-containing particles 2 increases and accordingly the oxygen storage capability improves.
- the Ce- and Zr-containing particles 2 in Example 2 which had a relatively small average particle diameter, exhibit highest oxygen storage capability.
- Example 5 the CeO 2 content and the ZrO 2 content in the material composition were 8.1% by mass and 1.0% by mass, respectively.
- the content of the Ce- and Zr-containing particles 2 was 9.1% by mass.
- the solid solubility rate of Zr was 11.7 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 130 nm.
- the oxygen storage capability was 0.0006 and high.
- Example 6 the CeO 2 content and the ZrO 2 content in the material composition were 8.0% by mass and 2.0% by mass, respectively.
- the content of the Ce- and Zr-containing particles 2 was 10.0% by mass.
- the solid solubility rate of Zr was 18.3 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 125 nm.
- the oxygen storage capability was 0.0008 and high.
- Example 7 the CeO 2 content and the ZrO 2 content in the material composition were 7.9% by mass and 3.0% by mass, respectively.
- the content of the Ce- and Zr-containing particles 2 was 10.9% by mass.
- the solid solubility rate of Zr was 16.1 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 126 nm.
- the oxygen storage capability was 0.0007 and high.
- Example 8 the CeO 2 content and the ZrO 2 content in the material composition were 7.8% by mass and 3.9% by mass, respectively.
- the content of the Ce- and Zr-containing particles 2 was 11.7% by mass.
- the solid solubility rate of Zr was 12.2 mol %.
- the Ce- and Zr-containing particles 2 had an average particle diameter of 128 nm.
- the oxygen storage capability was 0.0006 and high.
- Comparative Example 1 the CeO 2 content and the ZrO 2 content in the material composition were 8.1% by mass and 0.0% by mass, respectively. That is, in Comparative Example 1, the CeO 2 content in the material composition was approximately the same as the CeO 2 contents in Examples 2 and 5 to 8, and Zr was not included in the materials. In Comparative Example 1, the oxygen storage capability was 0.0005 and low.
- Comparative Example 2 the CeO 2 content and the ZrO 2 content in the material composition were 0.0% by mass and 0.0% by mass, respectively. That is, in Comparative Example 2, Ce and Zr were not included in the materials. In Comparative Example 2, the oxygen storage capability was 0.0000.
- the porous ceramic structure 1 includes the porous structure body (in the above-described example, the honeycomb structure 10 ) composed primarily of cordierite, and the Ce- and Zr-containing particles 2 fixedly attached to the structure body.
- the Ce- and Zr-containing particles 2 contain Ce and Zr.
- the Ce- and Zr-containing particles 2 have a fixedly attached portion 21 located inside the structure body and a protrusion 22 contiguous with the fixedly attached portion 21 and protruding from the structure body. This configuration improves promoter activity in the porous ceramic structure 1 as described above.
- catalytic particles i.e., fine catalytic particles 3
- the Ce- and Zr-containing particles 2 improve promoter activity in the porous ceramic structure 1 as described above
- the fine catalytic particles 3 improve catalytic activity.
- there is no need for processes such as a coating process described above in order to improve catalytic activity it is possible to prevent an increase in pressure loss caused by such a coating process. Accordingly, it is possible to achieve both high activation of the catalyst and a reduction in pressure loss in the porous ceramic structure 1 .
- the total Ce/Zr content is preferably higher than or equal to 6.0% by mass and lower than or equal to 20% by mass in terms of CeO 2 and ZrO 2 . This further improves promoter activity in the porous ceramic structure 1 as shown in Examples 1 to 8.
- the Ce content is preferably higher than or equal to 5.0% by mass and lower than or equal to 15% by mass in terms of CeO 2 . This further improves promoter activity in the porous ceramic structure 1 as shown in Examples 1 to 8.
- the Zr content is preferably higher than or equal to 1.0% by mass and lower than or equal to 5.0% by mass in terms of ZrO 2 . This further improves promoter activity in the porous ceramic structure 1 as shown in Examples 1 to 8.
- At least part of Ce in the porous ceramic structure 1 preferably exists as CeO 2 . This allows the porous ceramic structure 1 to exhibit favorable promoter activity.
- At least part of Zr in the porous ceramic structure 1 is preferably dissolved as a solid solution in CeO 2 .
- the ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO 2 with Zr dissolved therein as a solid solution is higher than or equal to 10% and lower than or equal to 20%. This further improves promoter activity in the porous ceramic structure 1 .
- the Ce- and Zr-containing particles 2 preferably have an average particle diameter greater than or equal to 10 nm and less than or equal to 2 ⁇ m.
- the Ce- and Zr-containing particles 2 with an average particle diameter greater than or equal to 10 nm can favorably support the fine catalytic particles 3 .
- the Ce- and Zr-containing particles 2 with an average particle diameter less than or equal to 2 ⁇ m increase the specific surface area of the Ce- and Zr-containing particles 2 exposed from the honeycomb structure 10 and favorably improve promoter activity in the porous ceramic structure 1 .
- porous ceramic structure 1 described above may be modified in various ways.
- the shapes of the Ce- and Zr-containing particles 2 are not limited to particulate shapes and may be any of other various shapes (e.g., fiber shape).
- the fixedly attached portions 21 of the Ce- and Zr-containing particles 2 do not necessarily have to exist at grain boundaries of the cordierite crystals 122 , and the protrusions 22 also do not necessarily have to protrude from the grain boundaries.
- the average particle diameter of the Ce- and Zr-containing particles 2 may be less than 10 nm, or may be greater than 2 ⁇ m.
- the total Ce/Zr content may be lower than 6.0% by mass or may be higher than 20% by mass in terms of CeO 2 and ZrO 2 .
- the Ce content may be lower than 5.0% by mass or may be higher than 15% by mass in terms of CeO 2 .
- the Zr content may be lower than 1.0% by mass or may be higher than 5.0% by mass in terms of ZrO 2 .
- the ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO 2 with Zr dissolved therein as a solid solution may be lower than 10% or may be higher than 20%.
- Zr does not necessarily have to be dissolved as a solid solution in CeO 2 .
- Ce may exist in a form other than CeO 2 .
- the shape of the structure body described above is not limited to a honeycomb shape, and may be any of various shapes other than the honeycomb shape (e.g., generally cylinder-like shape).
- the method of producing the porous ceramic structure 1 is not limited to the method described above, and may be modified in various ways.
- the porous ceramic structure 1 may be used in applications other than for use as a catalyst carrier for cleaning an exhaust gas.
- the porous ceramic structure according to the present invention is applicable as a catalyst carrier such as catalyst carrier for cleaning an automobile exhaust gas.
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Abstract
Description
- The present application claims the benefit of priority to Japanese Patent Application No. 2020-148171 filed on Sep. 3, 2020, the entire contents of which are incorporated herein by reference in its entirety.
- The present invention relates to a porous ceramic structure.
- A porous ceramic structure having a honeycomb structure has conventionally been used as a catalytic converter for use in processing for cleaning hazardous substances such as HC, CO, and NOx contained in an exhaust gas exhausted from an engine of an automobile or other vehicles. Such a porous ceramic structure may be subjected to, for example, a coating process using γ-alumina in order to increase a specific surface area and thereby increase the amount of a catalyst supported, but such a coating process may increase pressure loss in the structure.
- In view of this, Japanese Patent Application Laid-Open No. 2017-171543 (Document 1) proposes a technique that eliminates the need for the aforementioned coating process by exposing part of cerium dioxide particles from the surfaces of pores in a honeycomb structure and causing the cerium dioxide particles to support fine catalytic particles of an element of the platinum group. The cerium dioxide particles have oxygen storage and release capability and act as promoters that reduce variations in air-fuel ratio in an exhaust gas by storing or releasing oxygen and thereby maintain high catalytic activity of fine catalytic particles.
- Meanwhile, in recent years, various regulations for automobile exhaust gases are becoming more stringent, and there is demand for a further increase of catalytic activity in a catalytic converter.
- The present invention is intended for a porous ceramic structure, and it is an object of the present invention to improve promoter activity in the porous ceramic structure.
- A porous ceramic structure according to one preferable embodiment of the present invention includes a porous structure body composed primarily of cordierite, and Ce- and Zr-containing particles containing Ce and Zr and fixedly attached to the structure body. The Ce- and Zr-containing particles have a fixedly attached portion located inside the structure body, and a protrusion contiguous with the fixedly attached portion and protruding from the structure body.
- Accordingly, it is possible to improve promoter activity in the porous ceramic structure.
- Preferably, a total content of Ce and Zr is higher than or equal to 6.0% by mass and lower than or equal to 20% by mass in terms of CeO2 and ZrO2.
- Preferably, a Ce content is higher than or equal to 5.0% by mass and lower than or equal to 15% by mass in terms of CeO2.
- Preferably, a Zr content is higher than or equal to 1.0% by mass and lower than or equal to 5.0% by mass in terms of ZrO2.
- Preferably, at least part of Ce exists as CeO2.
- Preferably, at least part of Zr is dissolved as a solid solution in CeO2.
- Preferably, a ratio of an amount of substance of Zr to a total amount of substances of Ce and Zr in CeO2 with Zr dissolved therein as a solid solution is higher than or equal to 10% and lower than or equal to 20%.
- Preferably, the Ce- and Zr-containing particles have an average particle diameter greater than or equal to 10 nm and less than or equal to 2 μm.
- Preferably, catalyst particles are supported by the Ce- and Zr-containing particles.
- These and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
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FIG. 1 is a perspective view of a porous ceramic structure; -
FIG. 2 is a schematic diagram illustrating part of a partition wall in enlarged dimensions. -
FIG. 3 shows an SEM image of the surface of the partition wall; and -
FIG. 4 is a sectional view of an area in the vicinity of a Ce- and Zr-containing particle. -
FIG. 1 is a perspective view illustrating a porousceramic structure 1 according to one embodiment of the present invention. For example, the porousceramic structure 1 is a catalyst carrier for cleaning an exhaust gas used in the purification of an exhaust gas exhausted from an engine. InFIG. 1 , the number ofcells 13 illustrated, which will be described later, is smaller than an actual number. - The porous
ceramic structure 1 includes ahoneycomb structure 10 serving as a porous structure body, and Ce- and Zr-containing particles fixedly attached to thehoneycomb structure 10. The Ce- and Zr-containing particles are fine particles containing cerium (Ce) and zirconium (Zr). The Ce- and Zr-containing particles support oxidation catalyst particles such as the aforementioned precious metal (e.g., elements of the platinum group such as platinum (Pt) or palladium (Pd)). In the porousceramic structure 1, fine particles other than the Ce- and Zr-containing particles may be fixedly attached to thehoneycomb structure 10, in addition to the Ce- and Zr-containing particles. - The
honeycomb structure 10 includes a tubularouter wall 11 and apartition wall 12. The tubularouter wall 11 has a tubular shape extending in a longitudinal direction (i.e., substantially the right-left direction inFIG. 1 ). For example, the tubularouter wall 11 may have a circular shape in cross section perpendicular to the longitudinal direction, and may have any other shape such as a polygon. Thepartition wall 12 is provided in the interior of the tubularouter wall 11 and partitions the interior into a plurality ofcells 13. Thehoneycomb structure 10 is a cell structure whose interior is partitioned into a plurality ofcells 13 by thepartition wall 12. The tubularouter wall 11 and thepartition wall 12 are each made of a porous material. From the viewpoint of increasing the strength of the porousceramic structure 1, thepartition wall 12 has, for example, a thickness greater than or equal to 50 micrometers (μm), preferably greater than or equal to 100 μm, and more preferably greater than or equal to 150 μm. From the viewpoint of reducing pressure loss in thepartition wall 12, the thickness of thepartition wall 12 is, for example, less than or equal to 500 μm and preferably less than or equal to 450 μm. - Each
cells 13 is a space extending in the longitudinal direction and forms a flow path that passes an exhaust gas from an engine. For example, thecells 13 may have a polygonal (e.g., triangular, quadrangular, pentagonal, or hexagonal) shape in cross section perpendicular to the longitudinal direction, and may have any other shape such as a circle. Thecells 13 typically have the same cross-sectional shape. Alternatively, thecells 13 may includecells 13 that have different cross-sectional shapes. From the viewpoint of improving oxidation performance of the porousceramic structure 1, the density of the cells (cell density) is, for example, higher than or equal to 8 cells per square centimeters (cells/cm2) and preferably higher than or equal to 15 cells/cm2. From the viewpoint of reducing pressure loss, the cell density is, for example, lower than or equal to 95 cells/cm2 and preferably lower than or equal to 78 cells/cm2. - The
honeycomb structure 10 is composed primarily of cordierite (2MgO.2Al2O3.5SiO2). Thehoneycomb structure 10 may be composed of only cordierite, or may contain other materials different from cordierite (e.g., metal or ceramic other than cordierite). The content of cordierite in thehoneycomb structure 10 is, for example, higher than or equal to 75% by mass and preferably higher than or equal to 80% by mass. In the present embodiment, thehoneycomb structure 10 is substantially composed of only cordierite. - From the viewpoint of reducing pressure loss in the porous
ceramic structure 1, thepartition wall 12 of thehoneycomb structure 10 has, for example, an open porosity higher than or equal to 25%, preferably higher than or equal to 30%, and more preferably higher than or equal to 35%. From the viewpoint of ensuring the strength of the porousceramic structure 1, the open porosity of thepartition wall 12 is, for example, lower than or equal to 70% and preferably lower than or equal to 65%. The open porosity can be measured by, for example, the Archimedes method using deionized water as a medium. - The
partition wall 12 of thehoneycomb structure 10 has, for example, a mean pore diameter greater than or equal to 5 μm and preferably greater than or equal to 8 μm. Like the open porosity, pressure loss in the porousceramic structure 1 decreases as the mean pore diameter of thepartition wall 12 increases. From the viewpoint of improving catalytic activity in the porousceramic structure 1, the mean pore diameter of thehoneycomb structure 10 is, for example, less than or equal to 40 μm, preferably less than or equal to 30 μm, and more preferably less than or equal to 25 μm. The mean pore diameter can be measured by, for example, mercury porosimetry (compliant with JIS R1655). -
FIG. 2 is a schematic diagram illustrating part of thepartition wall 12 of the porousceramic structure 1 in enlarged dimensions. The aforementioned Ce- and Zr-containingparticles 2 are fixedly attached to the surface of thepartition wall 12 of thehoneycomb structure 10 in an exposed manner. The surface of thepartition wall 12 refers to the outer surface of the partition wall 12 (i.e., the surface surrounding the cells 13) and the inner surfaces of a large number of small pores in thepartition wall 12. InFIG. 2 , the Ce- and Zr-containingparticles 2 on the surface of thepartition wall 12 are cross-hatched. Moreover, finecatalytic particles 3 such as precious metal particles supported on the surface of the Ce- and Zr-containingparticles 2 are also illustrated inFIG. 2 . The Ce- and Zr-containingparticles 2 generally have particle diameters greater than the particle diameters of the finecatalytic particles 3. Note that the particle diameters of the Ce- and Zr-containingparticles 2 and the finecatalytic particles 3 inFIG. 2 are illustrated larger than actual particle diameters. - As described above, in the porous
ceramic structure 1, the finecatalytic particles 3 are supported by the Ce- and Zr-containingparticles 2 exposed to the surface of thepartition wall 12. This facilitates an increase in the amount of finecatalytic particles 3 supported, without increasing the specific surface area of thepartition wall 12 by a conventional coating process (wash coating) using γ-alumina. Therefore, it is possible to, for example, prevent an increase in pressure loss from being caused by a coating process using γ-alumina. It is not an absolute necessity that all of the finecatalytic particles 3 are supported by the Ce- and Zr-containingparticles 2, and some of the finecatalytic particles 3 may be supported directly on the surface of thehoneycomb structure 10. -
FIG. 3 shows a scanning electron microscope (SEM) image of the surface of thepartition wall 12 in thehoneycomb structure 10. In the porousceramic structure 1, the particulate Ce- and Zr-containing particles 2 (white portions in the image) are fixedly attached to the surface of thehoneycomb structure 10. For example, the Ce- and Zr-containingparticles 2 are fixedly attached to the grain boundaries of a large number of cordierite crystals 122 (gray portions in the image), which form thehoneycomb structure 10, and protrude (i.e., are exposed) from the surface of thehoneycomb structure 10 to the surrounding space.FIG. 3 is an illustration of a state before the aforementioned fine catalytic particles 3 (seeFIG. 2 ) are supported by the Ce- and Zr-containingparticles 2. -
FIG. 4 is a sectional view of an area in the vicinity of a Ce- and Zr-containingparticle 2 on the surface of thepartition wall 12 of thehoneycomb structure 10. As illustrated inFIG. 4 , the Ce- and Zr-containingparticle 2 is in a form partly protruding from the inside of thehoneycomb structure 10 to the surrounding space. InFIG. 4 , the aforementioned fine catalytic particles 3 (seeFIG. 2 ) supported on the Ce- and Zr-containingparticles 2 are not illustrated. - The Ce- and Zr-containing
particle 2 has a fixedly attachedportion 21 and aprotrusion 22. The fixedly attachedportion 21 is located inside thehoneycomb structure 10. The language “inside thehoneycomb structure 10” refers to inside the cordierite composing thehoneycomb structure 10 and does not refer to the internal spaces of small pores provided in thehoneycomb structure 10. The fixedly attachedportion 21 is a bonding portion of the Ce- and Zr-containingparticle 2 that is bonded to the cordierite serving as the principal component of thehoneycomb structure 10 and that is fixedly attached to the inside of the cordierite. In other words, the fixedly attachedportion 21 is a portion of the Ce- and Zr-containingparticle 2 that crawls into the cordierite from the surface of thehoneycomb structure 10 to the side opposite to the space around the surface. In yet other words, the fixedly attachedportion 21 is an area of the Ce- and Zr-containingparticle 2 that has a surface covered with the cordierite. To be more specific, the fixedly attachedportion 21 exists at a grain boundary of cordierite crystals 122 (FIG. 3 ) in thehoneycomb structure 10 and is fixedly attached to the grain boundary. - The
protrusion 22 is a portion of the Ce- and Zr-containingparticle 2 that protrudes from the surface of thehoneycomb structure 10 into the surrounding space. In other words, theprotrusion 22 is a portion exposed from the surface of the aforementioned cordierite. To be more specific, theprotrusion 22 protrudes from a grain boundary ofcordierite crystals 122 into the surrounding space. Theprotrusion 22 is contiguous with the fixedly attachedportion 21. - In the porous
ceramic structure 1, for example, some of a large number of Ce- and Zr-containingparticles 2 are fixedly attached to the surface of thehoneycomb structure 10 as described above, and the other Ce- and Zr-containingparticles 2 are located in their entirety inside thehoneycomb structure 10. Note that substantially all of the Ce- and Zr-containingparticles 2 may be fixedly attached to the surface of thehoneycomb structure 10. Since thehoneycomb structure 10 is not subjected to a coating process using γ-alumina or other materials as described above, there is no case that the Ce- and Zr-containingparticles 2 are fixedly attached to thehoneycomb structure 10 via a coating formed by such a coating process. - The Ce- and Zr-containing
particles 2 have, for example, an average particle diameter greater than or equal to 10 nm and less than or equal to 2 μm, preferably greater than or equal to 10 nm and less than or equal to 500 nm, and more preferably greater than or equal to 10 nm and less than or equal to 200 nm. The average particle diameter of the Ce- and Zr-containingparticles 2 is an average particle diameter of theprotrusions 22 of the Ce- and Zr-containingparticles 2 that can be observed with an SEM. For example, the average particle diameter of the Ce- and Zr-containingparticles 2 is obtained by calculating an average value of the particle diameters of Ce- and Zr-containingparticles 2 in an image of the Ce- and Zr-containingparticles 2 captured with a predetermined magnification using an SEM or a field emission SEM (FE-SEM) or a transmission electron microscope (TEM). Alternatively, a crystallite diameter of the Ce- and Zr-containingparticles 2 obtained by X-ray diffraction (XRD) may be regarded as an average particle diameter of the Ce- and Zr-containingparticles 2. - A total content of Ce and Zr in the porous
ceramic structure 1 is, for example, higher than or equal to 6.0% by mass and lower than or equal to 20% by mass in terms of CeO2 and ZrO2. In the following description, the total content of Ce and Zr in the porousceramic structure 1 is also simply referred to as a “total Ce/Zr content.” The total Ce/Zr content is preferably higher than or equal to 8.0% by mass and lower than or equal to 15% by mass in terms of CeO2 and ZrO2. The total Ce/Zr content in terms of CeO2 and ZrO2 refers to the percentage of a value obtained by dividing the total mass of CeO2 and ZrO2 by the mass of the porousceramic structure 1 on the assumption that all Ce components contained in the porousceramic structure 1 exist as CeO2 and all Zr components contained in the porousceramic structure 1 exist as ZrO2. - The content of Ce in the porous
ceramic structure 1 is, for example, higher than or equal to 5.0% by mass and lower than or equal to 15% by mass in terms of CeO2. In the following description, the content of Ce in the porousceramic structure 1 is also simply referred to as a “Ce content.” The Ce content is preferably higher than or equal to 7.0% by mass and lower than or equal to 12% by mass in terms of CeO2. The Ce content in terms of CeO2 refers to the percentage of a value obtained by dividing the mass of CeO2 by the mass of the porousceramic structure 1 on the assumption that all Ce components contained in the porousceramic structure 1 exist as CeO2. - The content of Zr in the porous
ceramic structure 1 is, for example, higher than or equal to 1.0% by mass and lower than or equal to 5.0% by mass in terms of ZrO2. In the following description, the content of Zr in the porousceramic structure 1 is also simply referred to as a “Zr content.” The Zr content is preferably higher than or equal to 2.0% by mass and lower than or equal to 4.0% by mass in terms of ZrO2. The Zr content in terms of ZrO2 refers to the percentage of a value obtained by dividing the mass of ZrO2 by the mass of the porousceramic structure 1 on the assumption that all Zr components contained in the porousceramic structure 1 exist as ZrO2. - In the porous
ceramic structure 1, the Zr content in terms of ZrO2 is, for example, higher than or equal to 10% and lower than or equal to 40% of the Ce content in terms of CeO2 and is preferably higher than or equal to 20% and lower than or equal to 35% of the Ce content in terms of CeO2. - At least some of Ce components contained in the porous
ceramic structure 1 exist as CeO2. Preferably, substantially a total amount of Ce contained in the porousceramic structure 1 exists as CeO2. At least some of Zr components contained in the porousceramic structure 1 are dissolved as a solid solution in CeO2. Preferably, substantially all Zr components contained in the porousceramic structure 1 are dissolved as a solid solution in CeO2. A ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO2 with Zr dissolved therein as a solid solution is, for example, higher than or equal to 10% and lower than or equal to 20% (i.e., higher than or equal to 10 mol % and lower than or equal to 20 mol %). This ratio is preferably higher than or equal to 15% and lower than or equal to 20%. - The aforementioned CeO2 stores and releases oxygen due to a reaction expressed by
Expression 1 below. The reaction from the left-hand side to the right-hand side inExpression 1 indicates the reaction of CeO2 that releases oxygen, and the reaction from the right-hand side to the left-hand side indicates the reaction of CeO2 that stores oxygen. In this way, CeO2 has oxygen storage and release capability and acts as a promoter that reduces variations in air-fuel ratio in the exhaust gas by storing or releasing oxygen and thereby maintains high catalytic activity of the fine catalytic particles 3 (seeFIG. 2 ). -
CeO2=CeO2 −x+(x/2)O2 (Expression 1) - The porous
ceramic structure 1 may be produced by any of various known methods. For example, first, a structure raw material is prepared by weighing and mixing materials for thehoneycomb structure 10 and materials for the Ce- and Zr-containingparticles 2. The materials for thehoneycomb structure 10 are composed primarily of a raw material for cordierite that serves as an aggregate of thehoneycomb structure 10 and include, for example, magnesium oxide (MgO), aluminum oxide (Al2O3), or silicon oxide (SiO2). The materials for thehoneycomb structure 10 also include, for example, a bore-forming agent and a binder. The materials for the Ce- and Zr-containingparticles 2 are, for example, CeO2 and ZrO2. After the structure raw material is dry mixed in a kneader, water is charged and the structure raw material is further kneaded in the kneader to prepare a green body. The amounts of time required for the dry mixing and the kneading described above may, for example, be 15 minutes and 30 minutes, respectively. The dry mixing time and the kneading time may be modified in various ways. - In the example described above, CeO2 and ZrO2 are individually added to the aggregate and the like of the
honeycomb structure 10, but the method of the addition may be modified in various ways. For example, a material generated by immersing Zr in CeO2 and drying and firing a resultant compound may be added to the aggregate and the like of thehoneycomb structure 10. In this material, part of Zr may be dissolved as a solid solution in CeO2, or may adhere to CeO2. - The aforementioned green body is molded into a columnar shape by a vacuum kneading machine or any other machine and then extruded and molded into a honeycomb compact of a honeycomb shape by an extruder. The honeycomb compact includes therein a grid-like partition wall that sections the honeycomb compact into a plurality of cells serving as flow paths for a fluid such as an exhaust gas. Note that the honeycomb compact may be molded by a molding method other than extrusion molding.
- Then, the honeycomb compact is subjected to drying. There are no particular limitations on the method of drying the honeycomb compact. Examples of the drying method include hot air drying, microwave drying, dielectric drying, reduced pressure drying, vacuum drying, and freeze drying, and may also include any combination of these drying methods. For example, the honeycomb compact is subjected to microwave drying so as to evaporate approximately 50% to 80% of moisture, and is then subjected to hot air drying (at 60° C. to 100° C. for 6 to 20 hours). Preferably, the honeycomb compact is subjected to microwave drying so as to evaporate approximately 70% of moisture, and is then subjected to hot air drying (at 80° C. for 12 hours). Then, the honeycomb compact is put into a degreasing furnace that is maintained at 450° C. so as to remove (i.e., degrease) organic components remaining in the honeycomb compact.
- Thereafter, the honeycomb compact is subjected to a firing process (firing) so as to form the porous
ceramic structure 1 including thehoneycomb structure 1 and the Ce- and Zr-containingparticles 2. For example, the firing process is conducted at a firing temperature of 1300° C. to 1500° C. for 8 hours under atmospheric pressure. The firing temperature is preferably higher than or equal to 1350° C. and more preferably higher than or equal to 1370° C. The firing temperature is also preferably lower than or equal to 1450° C. and more preferably lower than or equal to 1430° C. Conditions for the firing process may be modified appropriately. The finecatalytic particles 3 are to be supported after the firing process described above. - Next, examples of the porous
ceramic structure 1 described above and porous ceramic structures according to comparative examples for comparison with the porousceramic structure 1 will be described with reference to Tables 1 and 2. Numeric values or the like in Tables 1 and 2 indicate values for porousceramic structures 1 before the finecatalytic particles 3 are supported (i.e.,honeycomb structures 10 with the Ce- and Zr-containingparticles 2 fixedly attached). -
TABLE 1 Material Composition (mass %) MgO Al2O3 SiO2 CeO2 ZrO2 Total Example 1 12.9 31.8 47.2 6.1 2.0 100.0 Example 2 12.6 30.9 45.9 7.9 2.6 100.0 Example 3 12.3 30.1 44.7 9.6 3.2 100.0 Example 4 11.9 29.4 43.6 11.3 3.8 100.0 Example 5 12.8 31.5 46.7 8.1 1.0 100.0 Example 6 12.7 31.2 46.2 8.0 2.0 100.0 Example 7 12.5 30.8 45.8 7.9 3.0 100.0 Example 8 12.4 30.5 45.3 7.8 3.9 100.0 Comparative 12.9 31.8 47.2 8.1 0.0 100.0 Example 1 Comparative 14.1 34.6 51.3 0.0 0.0 100.0 Example 2 -
TABLE 2 Ce- and Zr-Containing Solid Solubility Average Particle Diameter Oxygen Particles Rate of Zr of Ce—Zr-Containing Storage (mass %) (mol %) Particles(nm) Capability Example 1 8.1 17.2 55 0.0007 Example 2 10.6 18.3 120 0.0008 Example 3 12.9 17.8 630 0.0007 Example 4 15.0 17.2 1200 0.0006 Example 5 9.1 11.7 130 0.0006 Example 6 10.0 18.3 125 0.0008 Example 7 10.9 16.1 126 0.0007 Example 8 11.7 12.2 128 0.0006 Comparative 0.0 0.0 — 0.0005 Example 1 Comparative — — — 0.0000 Example 2 - In Table 1, the content of each component (mass %) in the composition of the materials for the porous
ceramic structure 1 was calculated through analysis based on inductivity coupled plasma (ICP) atomic emission spectroscopy. In Table 2, the content (mass %) of the Ce- and Zr-containingparticles 2 refers to a total of the contents (mass %) of CeO2 and ZrO2. - In Table 2, the ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO2 with Zr dissolved therein as a solid solution (hereinafter, also referred to as “solid solubility rate of Zr”) was obtained as follows. First, X-ray diffraction data obtained by measuring the porous
ceramic structure 1 with an X-ray diffractometer (rotary anti-cathode X-ray diffractometer: RINT produced by Rigaku Corporation) was analyzed to obtain a lattice constant of CeO2. Then, calibration curves were created for lattice constants obtained in the same manner for samples having known solid solubility of Zr, and the solid solubility rate of Zr (mol %) was obtained using the calibration curves. - In Table 2, the average particle diameter of the Ce- and Zr-containing
particles 2 in the porousceramic structure 1 is an arithmetical mean of the particle diameters of the Ce- and Zr-containingparticles 2 measured from the aforementioned SEM image. - In Table 2, the oxygen storage capability of the porous
ceramic structure 1 was obtained as follows. First, the porousceramic structure 1 was placed in a container, and a first gas containing oxygen (O2) is supplied to the internal space of the container to oxidize the Ce- and Zr-containingparticles 2 and store oxygen. The first gas was a mixed gas of O2 and an inert gas such as nitrogen (N2), and the content of O2 in the mixed gas was assumed to be 20% by volume. Then, the first gas was exhausted from the internal space of the container, and a second gas containing H2 was supplied to the internal space and passed through a large number ofcells 13 in the porousceramic structure 1. The second gas was a mixed gas of H2 and an inert gas such as N2, and the H2 content in the mixed gas was assumed to be 5% by volume. - In the second gas, H2 reacted with the oxygen released from the Ce- and Zr-containing particles 2 (i.e., oxygen stored in the Ce- and Zr-containing
particles 2 as a result of supply of the first gas) to form H2O when passing through thecells 13. Thus, if the amount of H2O of the second gas passing through the porousceramic structure 1 is measured by gas chromatography or other techniques, the amount of oxygen stored in the Ce- and Zr-containingparticles 2 can be calculated from a resultant measurement value. Table 1 lists, as the oxygen storage capability of the porousceramic structures 1, the value obtained by dividing the amount of substance (mol) of O2 calculated from the measurement value of H2O in the second gas by the amount of substance (mol) of Ce contained in the porousceramic structures 1. As the oxygen storage capability improves, the Ce- and Zr-containingparticles 2 have higher oxygen storage and release capability and, as described above, have a higher function of reducing variations in air-fuel ratio in the exhaust gas. That is, the Ce- and Zr-containingparticles 2 exhibit higher promoter activity as the oxygen storage capability improves. - In Example 1, the CeO2 content and the ZrO2 content in the material composition were 6.1% by mass and 2.0% by mass, respectively. The ZrO2 content was approximately one third of the CeO2 content. The content of the Ce- and Zr-containing
particles 2 was 8.1% by mass. The solid solubility rate of Zr was 17.2 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 55 nm. The oxygen storage capability was 0.0007 and high. - In Example 2, the CeO2 content and the ZrO2 content in the material composition were 7.9% by mass and 2.6% by mass, respectively. The ZrO2 content was approximately one third of the CeO2 content. The content of the Ce- and Zr-containing
particles 2 was 10.6% by mass. The solid solubility rate of Zr was 18.3 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 120 nm. The oxygen storage capability was 0.0008 and high. - In Example 3, the CeO2 content and the ZrO2 content in the material composition were 9.6% by mass and 3.2% by mass, respectively. The ZrO2 content was approximately one third of the CeO2 content. The content of the Ce- and Zr-containing
particles 2 was 12.9% by mass. The solid solubility rate of Zr was 17.8 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 630 nm. The oxygen storage capability was 0.0007 and high. - In Example 4, the CeO2 content and the ZrO2 content in the material composition were 11.3% by mass and 3.8% by mass, respectively. The ZrO2 content was approximately one third of the CeO2 content. The content of the Ce- and Zr-containing
particles 2 was 15.0% by mass. The solid solubility rate of Zr was 17.2 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 1200 nm. The oxygen storage capability was 0.0006 and high. - Comparisons of Example 1 to 4 show that the content of the Ce- and Zr-containing
particles 2 increases in order of Examples 1 to 4 and the average particle diameter of the Ce- and Zr-containingparticles 2 increases in the order of Examples 1 to 4. In the porousceramic structure 1, as the content of the Ce- and Zr-containingparticles 2 increases, the amount of storage of oxygen and the amount of release of oxygen, caused by the reaction expressed byExpression 1 above, increase and accordingly the oxygen storage capability improves. Moreover, as the average particle diameter of the Ce- and Zr-containingparticles 2 decreases, the surface area of the Ce- and Zr-containingparticles 2 increases and accordingly the oxygen storage capability improves. In Examples 1 to 4, the Ce- and Zr-containingparticles 2 in Example 2, which had a relatively small average particle diameter, exhibit highest oxygen storage capability. - In Example 5, the CeO2 content and the ZrO2 content in the material composition were 8.1% by mass and 1.0% by mass, respectively. The content of the Ce- and Zr-containing
particles 2 was 9.1% by mass. The solid solubility rate of Zr was 11.7 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 130 nm. The oxygen storage capability was 0.0006 and high. - In Example 6, the CeO2 content and the ZrO2 content in the material composition were 8.0% by mass and 2.0% by mass, respectively. The content of the Ce- and Zr-containing
particles 2 was 10.0% by mass. The solid solubility rate of Zr was 18.3 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 125 nm. The oxygen storage capability was 0.0008 and high. - In Example 7, the CeO2 content and the ZrO2 content in the material composition were 7.9% by mass and 3.0% by mass, respectively. The content of the Ce- and Zr-containing
particles 2 was 10.9% by mass. The solid solubility rate of Zr was 16.1 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 126 nm. The oxygen storage capability was 0.0007 and high. - In Example 8, the CeO2 content and the ZrO2 content in the material composition were 7.8% by mass and 3.9% by mass, respectively. The content of the Ce- and Zr-containing
particles 2 was 11.7% by mass. The solid solubility rate of Zr was 12.2 mol %. The Ce- and Zr-containingparticles 2 had an average particle diameter of 128 nm. The oxygen storage capability was 0.0006 and high. - Comparisons of Examples 5 to 8 show that the CeO2 content in the material composition was set to approximately 8% by mass, and the ZrO2 content in the material composition was incremented by approximately 1.0% by mass from 1.0% by mass to 3.9% by mass. As a result, the solid solubility rate of Zr was highest in Example 6 and was second highest in Example 7. The oxygen storage capability was also highest in Example 6 and was second highest in Example 7. In Examples 5 to 8, the Ce- and Zr-containing
particles 2 had an average particle diameter of 125 nm to 130 nm, i.e., had an approximately the same average particle diameter. - In Comparative Example 1, the CeO2 content and the ZrO2 content in the material composition were 8.1% by mass and 0.0% by mass, respectively. That is, in Comparative Example 1, the CeO2 content in the material composition was approximately the same as the CeO2 contents in Examples 2 and 5 to 8, and Zr was not included in the materials. In Comparative Example 1, the oxygen storage capability was 0.0005 and low.
- In Comparative Example 2, the CeO2 content and the ZrO2 content in the material composition were 0.0% by mass and 0.0% by mass, respectively. That is, in Comparative Example 2, Ce and Zr were not included in the materials. In Comparative Example 2, the oxygen storage capability was 0.0000.
- As described above, the porous
ceramic structure 1 includes the porous structure body (in the above-described example, the honeycomb structure 10) composed primarily of cordierite, and the Ce- and Zr-containingparticles 2 fixedly attached to the structure body. The Ce- and Zr-containingparticles 2 contain Ce and Zr. The Ce- and Zr-containingparticles 2 have a fixedly attachedportion 21 located inside the structure body and aprotrusion 22 contiguous with the fixedly attachedportion 21 and protruding from the structure body. This configuration improves promoter activity in the porousceramic structure 1 as described above. - Preferably, in the porous
ceramic structure 1, catalytic particles (i.e., fine catalytic particles 3) are supported on the Ce- and Zr-containingparticles 2. Since the Ce- and Zr-containingparticles 2 improve promoter activity in the porousceramic structure 1 as described above, the finecatalytic particles 3 improve catalytic activity. Moreover, there is no need for processes such as a coating process described above in order to improve catalytic activity, it is possible to prevent an increase in pressure loss caused by such a coating process. Accordingly, it is possible to achieve both high activation of the catalyst and a reduction in pressure loss in the porousceramic structure 1. - As described above, in the porous
ceramic structure 1, the total Ce/Zr content is preferably higher than or equal to 6.0% by mass and lower than or equal to 20% by mass in terms of CeO2 and ZrO2. This further improves promoter activity in the porousceramic structure 1 as shown in Examples 1 to 8. - As described above, in the porous
ceramic structure 1, the Ce content is preferably higher than or equal to 5.0% by mass and lower than or equal to 15% by mass in terms of CeO2. This further improves promoter activity in the porousceramic structure 1 as shown in Examples 1 to 8. - As described above, in the porous
ceramic structure 1, the Zr content is preferably higher than or equal to 1.0% by mass and lower than or equal to 5.0% by mass in terms of ZrO2. This further improves promoter activity in the porousceramic structure 1 as shown in Examples 1 to 8. - As described above, at least part of Ce in the porous
ceramic structure 1 preferably exists as CeO2. This allows the porousceramic structure 1 to exhibit favorable promoter activity. - As described above, at least part of Zr in the porous
ceramic structure 1 is preferably dissolved as a solid solution in CeO2. This allows the porousceramic structure 1 to exhibit favorable promoter activity. More preferably, the ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO2 with Zr dissolved therein as a solid solution is higher than or equal to 10% and lower than or equal to 20%. This further improves promoter activity in the porousceramic structure 1. - As described above, the Ce- and Zr-containing
particles 2 preferably have an average particle diameter greater than or equal to 10 nm and less than or equal to 2 μm. The Ce- and Zr-containingparticles 2 with an average particle diameter greater than or equal to 10 nm can favorably support the finecatalytic particles 3. Moreover, the Ce- and Zr-containingparticles 2 with an average particle diameter less than or equal to 2 μm increase the specific surface area of the Ce- and Zr-containingparticles 2 exposed from thehoneycomb structure 10 and favorably improve promoter activity in the porousceramic structure 1. - The porous
ceramic structure 1 described above may be modified in various ways. - For example, the shapes of the Ce- and Zr-containing
particles 2 are not limited to particulate shapes and may be any of other various shapes (e.g., fiber shape). The fixedly attachedportions 21 of the Ce- and Zr-containingparticles 2 do not necessarily have to exist at grain boundaries of thecordierite crystals 122, and theprotrusions 22 also do not necessarily have to protrude from the grain boundaries. - The average particle diameter of the Ce- and Zr-containing
particles 2 may be less than 10 nm, or may be greater than 2 μm. - In the porous
ceramic structure 1, the total Ce/Zr content may be lower than 6.0% by mass or may be higher than 20% by mass in terms of CeO2 and ZrO2. The Ce content may be lower than 5.0% by mass or may be higher than 15% by mass in terms of CeO2. The Zr content may be lower than 1.0% by mass or may be higher than 5.0% by mass in terms of ZrO2. - In the porous
ceramic structure 1, the ratio of the amount of substance of Zr to the total amount of substances of Ce and Zr in CeO2 with Zr dissolved therein as a solid solution may be lower than 10% or may be higher than 20%. Note that Zr does not necessarily have to be dissolved as a solid solution in CeO2. Also, Ce may exist in a form other than CeO2. - In the porous
ceramic structure 1, the shape of the structure body described above is not limited to a honeycomb shape, and may be any of various shapes other than the honeycomb shape (e.g., generally cylinder-like shape). - The method of producing the porous
ceramic structure 1 is not limited to the method described above, and may be modified in various ways. - The porous
ceramic structure 1 may be used in applications other than for use as a catalyst carrier for cleaning an exhaust gas. - The configurations of the above-described preferred embodiments and variations may be appropriately combined as long as there are no mutual inconsistencies.
- While the invention has been shown and described in detail, the foregoing description is in all aspects illustrative and not restrictive. It is therefore to be understood that numerous modifications and variations can be devised without departing from the scope of the invention.
- The porous ceramic structure according to the present invention is applicable as a catalyst carrier such as catalyst carrier for cleaning an automobile exhaust gas.
- 1 Porous ceramic structure
- 2 Ce- and Zr-containing particles
- 3 Fine catalytic particles
- 10 Honeycomb structure
- 21 Fixedly attached portion
- 22 Protrusion
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